General Paradigm in Photoredox Nickel-Catalyzed Cross-Coupling Allows for Light-Free Access to Reactivity.,Angewandte Chemie International Edition

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General Paradigm in Photoredox Nickel-Catalyzed Cross-Coupling Allows for Light-Free Access to Reactivity.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-03-19 , DOI: 10.1002/anie.201916398
Rui Sun ₁ , Yangzhong Qin ₁ , Daniel G Nocera ₁

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Self‐sustained Ni^I/III cycles are established as a potentially general paradigm in photoredox Ni‐catalyzed carbon–heteroatom cross‐coupling reactions through a strategy that allows us to recapitulate photoredox‐like reactivity in the absence of light across a wide range of substrates in the amination, etherification, and esterification of aryl bromides, the latter of which has remained, hitherto, elusive under thermal Ni catalysis. Moreover, the accessibility of esterification in the absence of light is especially notable because previous mechanistic studies on this transformation under photoredox conditions have unanimously invoked energy‐transfer‐mediated pathways.

中文翻译：

Photoredox镍催化交叉偶联的一般范例可实现无光访问反应。

自我维持的Ni ^{I / III}循环被确立为光氧化还原Ni催化的碳-杂原子交叉偶联反应中的潜在一般范式，其策略是使我们能够在没有光的情况下在各种各样的底物上重现类似光氧化还原的反应性。在芳基溴化物的胺化，醚化和酯化反应中，迄今为止，后者在热镍催化下仍然难以捉摸。此外，在没有光照的情况下酯化的可及性尤其显着，因为先前在光氧化还原条件下对该转化进行的机理研究一致地调用了能量转移介导的途径。

更新日期：2020-03-19

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